Hair treating composition and method of use for setting



HAIR TREATlNG COMPOSITION AND METHOD OF USE FGR SETTING Virgil A. Gant, Oak Park, llll., assignor to Northwestern Research Corp, Chicago, ill, a corporation of illinois No Drawing. Application April 30, 1952,

Serial No. 235,330

4 Claims. c1. 1s2 7 This invention relates to the treatment of hair on the head of a human for the purposes of straightening kinky hair, curling hair after it has been straightened out, or for curling hair generally without harm to the hair or irritation either to the user or to the operator.

More particularly, this invention relates to a hairtreating composition and to the method of using the composition in the treatment of hair, and it comprises a continuation-in-part of my copending application, Serial No. 263,509, filed on December 26, 1951, now Patent No. 2,643,375, issued on June 23, 1953, which is a continuation-in-part of an application Serial No. 112,186, filed on August 24, 1949, now abandoned.

One of the popular methods presently used for hair treatment permanently to modify its arrangement comprises the application of compositions embodying substances which render the hair soft and plastic by reduction reaction to rupture the disulphide linkages in the keratin molecule which constitutes one of the fibrous proteins of which the hair is formed. While the hair is in this plastic condition, it can be formed readily to any desired configuration, such as into curls, by Winding about a curling spool or the like. Rupture of the disulphide linkage of the cystine molecule of the keratin is secured by a reduction reaction with thioglycolic acid. After the hair has been shaped or arranged to the desired position, the disulphide bond must be reformed through oxidation, as by the application of peroxide or other oxidizing materials. Suitable reducing agents also include salts of thioglycolic acid, and various metal sulphides.

Considerable difficulty has been experienced in the use of these compositions because compounds which rupture the disulphide bond by reduction reaction also may be used as depilatories for removing hair, the only difference between hair removal and hair softening residing in a small difference in pH of the treating composition.

Whether or not the treating composition operates as a depilatory or as a waving composition also depends in part upon the individual characteristics of the hair and the environment in which it is used. As a result, cold- Wave compositions of the type described have been found to be dangerous in many instances, especially when applied by inexperienced operators. Furthermore, in order to accomplish the desired results, especially for removing kinks from hair, hours of treatment may be required, and even then the end result may be insuflicient.

There are a number of other techniques which have been used in the past in the treatment of hair. However, in many respects the compositions involved in their use are even more objectionable than the cold-wave compositions heretofore described. For example, com

positions containing phenol formaldehyde resin and the like have been applied to the hair and then the phenol formaldehyde reacted to an advanced stage of polymeric growth to form the resinous compound on the hair shaft in a manner to encase the hair shaft and hold it straight. Reaction of phenol with formaldehyde in the presence of the hair filaments has been found to take place in combination with molecules existing in the hair itself whereby the reaction causes modification of the hair molecules to form a product which is different than normal hair. In addition, the phenolic material has been found to cause skin irritation and the reaction products resulting from such treatment are characterized by a yellow discoloration which is highly objectionable.

An older process which includes combing the hair with pressing oils has been found to be very undesirable and unsuitable because it is incapable of giving the desired results, and also provides for an unnaturally shiny appearance. The effect from combing hair with pressing oil is lost substantially immediately when the hair becomes moistened or wetted, and the eifects are lost very quickly even in the absence of moisture.

In accordance with the practice of this invention, the desired effect in hair straightening or permanent hair arrangement is achieved quickly, safely, and easily by the treatment of the hair on a human head with a composition containing an organic lubricant in combination with an organo-silicon polymer (polysiloxane) adapted to be set in contact with the surface of the hair as by elimination of diluent when the organo-silicon polymer is applied in an advanced stage of polymeric growth, or by reaction of the organo-silicon resin-forming composition, when applied in an intermediate stage of polymeric growth, to an advanced stage by activation through a catalyst or by heating to form a hardened and cured organo-silicon polymer.

The organo-silicon compounds applied and/or reacted on the hair in the manner described are not harmful to the hair or to the scalp. These compounds are characterized by excellent water-repellency which properties are transmitted to the hair strands with the result that they are relatively unafiected by moisture for a reason able time after setting. Thus the treatment with compositions of the type described provides for a relatively permanent arrangement of hair fibers even in the presence of high humidity or contact with moisture. The organo-silicon compounds are stable at relatively high temperatures and substantially colorless, so that their presence in the hair remains undetected and the natural color of the hair continues to be there. In fact, such organo-silicon compounds have been found to have a very favorable effect upon the sheen and appearance of the hair with the result that the treated hair becomes more attractive and the need for oils, sheen-producing agents and other pomades is eliminated. In general, these organo-silicon compounds function as protective agents for the hair without modifying the natural characteristics or the composition thereof while imparting permanent setting in any desired position.

Suitable organo-silicon compounds are selected of substances having the general formula wherein R generally is formed of a monovalent organic radical usually connected directly to the silicon atom through a contained carbon atom, and when the organic group of the R radical is of sufiicient length or molecular weight to resist hydrolysis, the R group may be connected through an oxygen atom and be in the form of a nonhydrolyzable oxy group. R is usually methyl, ethyl, propyl, phenyl, or benzyl, but it may also constitute any one of a large number of aliphatic, aromatic, mixed aliphaticaromatic, or heterocyclic groups, such as methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, cetyl to octadecyl, and higher, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl,

mcsityl, monoethyl phenyl, diethyl phenyl, naphthyl, methyl naphthyl, benzyl, phenyl ethyl, furfuryl, and the like. When aliphatic or mixed aliphatic-aromatic, the aliphatic group may be branched or straight-chained, it may be substituted or unsubstituted, and it may be saturated or unsaturated, such as in allyl, methallyl, vinyl, or acrylic groups.

If the original silane of which the organo-silicon polymer is formed contains more than two hydrolyzable groups, a cross-linked polymer can be produced which, when carried to the full extent of polymeric growth as by catalytic reaction or by heat or by combinations thereof, a product is secured which is substantially infusible and insoluble after treatment.

An organo-silicon material suitable for use in the practice of this invention which relies upon heat to advance the organo-silicon polymer to a group stage may be defined more appropriately by its characteristics which permit its use without injury to the hair. More specifically, it is desired to employ an organo-silicon resin forming material capable of reaction to an advanced stage at a temperature below 500 F. and preferably at a temperature between 256 and 400 F. At these temperatures it is possible to achieve polymerization in from one-half to three minutes, although more time may be necessary, depending upon the diluent present and the method of handling. Resinous materials which may be used in an intermediate stage of polymeric growth for subsequent polymerization on the hair or in a full stage of polymeric growth for setting by the elimination of diluent may be represented by compositions prepared in accordance with United States Patents Nos. 2,258,221, 2,371,068, 2,389,477, 2,371,050, 2,375,998, and British Patent No. 542,655.

In the absence of heat, the desired polymerization of the resin-forming material may be achieved by catalysts which cause polymerization to take place under conditions of use or at slightly elevated temperatures. Such catalysts may be incorporated directly into the hair-treating compositions in the event that reaction depends also upon the elimination of solvents or upon the availability of oxidation from the atmosphere, or it may be incorporated into the treating composition immediately before application to the hair in the event that reaction starts substantially immediately upon the addition. Condensation catalysts may be used if added just prior to application of the treating composition for use. Representative of catalytic agents are ethyl borate, ethylene diamine, triethanolamine, the naphthenates of cobalt, manganese, calcium and the like.

When relying on evaporation of solvent or of the aqueous medium in the organo-silicon compound for purposes of setting the organo-silicon compound on the hair, use may be made of an organo-siiicon resin having a large number of building units as previously described so as to be substantially solid at room temperature. Where setting by the elimination of diluent, such as solvents or water, is relied upon, temperatures considerably lower than those previously specified for chemical reaction may be used.

Suitable organo-silicon resins and resin-forming materials include the copolymers of phenyl methyl, phenyl and methyl polysiloxane, dimethyl, phenyl and methyl polysiloxanes, diphenyl methyl polysiloxane, methyl and phenyl polysiloxane, methyl and ethyl polysiloxane, and other condensation reaction products of hydrolyzed silanes, components of which have two or more hydrolyzable groups to permit a certain amount of cross-linking in resin formation.

These materials are preferably applied to the hair in dilute concentrations such as in solution with suitable solvents or in dispersions or emulsions with certain solvent or aqueous systems, alone or in combination. Suitable solvents for the organo-silicon compounds include toluene, xylene, benzene, coal tar naphtha, petroleum naphtha, chlorinated hydrocarbons such as carbon tetrachloride, ethylene dichloride and the like, alcohols such as ethanol, butanol, isopropyl alcohol, amyl alcohol and suitable non-toxic ethers and esters, such as cellosolve and the like. Preferred solvents should evaporate in from 0.1-5 minutes at the temperature of treatment, yet they should exhibit low vapor pressure or slow evaporation at room temperature to permit uniform distribution of the treating composition before the diluent escapes. The solvent system should have a flash point sufiiciently high to minimize the hazards and components of the system should be free of toxicity or skin irritation. Best use is made of glycol ethers and glycol esters such as ethylene glycol monoethyl ether and ethylene glycol monoethyl ether acetate as the solvent medium.

It is preferred to apply the treating composition by spraying from an atomizer into the particular area of hair being worked. Instead, the entire head may be wet with the composition if the diluent is of the type which does not evaporate before uniform distribution is secured. Application may also be made by a dabber or applicator on sections of the hair or the entire head may be wet by dipping into a bath of the treating composition or by flowing the substance over the desired area.

The amount of organo-silicon resin in the treating composition is preferentially maintained within the range of 1-3 percent by weight. Larger amounts up to 5 percent by weight may be used without difliculty unless an undesirable matting or bonded relation is caused, or unless the hair becomes increased in diameter and stiffened to a degree where it would become unmanageable or embrittled sufliciently to permit hair breakage. Some hair will'tolerate application of compositions containing more than 5 percent of the organo-silicon resinous material, but amounts in excess of 10 percent by weight are not practical from the use standpoint as well as the cost standpoint. When matting or stiffness results from the use of compositions containing more than three to five percent of organo-silicon resin, the undesirable effects thereof may be compensated in part by further addition of lubricant or other softening agents of the type which will be hereinafter described.

When the organo-silicon resinous component is embodied as a dispersion in .an aqueous medium, it is preferred to make use of a lubricant in combination therewith which is water-soluble and which is capable of becoming insoluble in water upon drying to impart the desired water repellency while still providing the desired sheen and softness to the hair shaft. Such materials soluble in the aqueous medium and insolubie upon drying may be and are preferably selected of compounds having the characteristics also of a surface active agent which improves the stability of the composition and increases the ability of the treating composition to wet out the surface of the hair fibers. Compounds of the type described may be selected of the Werner complex compound in which an acido group having more than 10 carbon atoms is coordinated with a trivalent nuclear chromium atom, such for example as stearato chromic chloride or corresponding chromic salts wherein the acido group is formed of fatty acids of the type of palmitic acid, oleic acid, cotton seed oil acid, tallow acid, and the like. Other compounds which may be used are fully described in the Iler Patent No. 2,273,040 which issued on February 17, 1942.

Instead of the Werner complex compound, use may be made of the water-soluble amine salts or cationic amine compounds wherein a fatty acid group having carbon lengths greater than 10 form at least one of the groups attached to the base amine. Representative are amine and cationic compounds of the type described in the Sloan Patent No. 2,356,542. Suchv compounds include dicoco di-metal ammonium chloride, di-dodecyl ammonium chloride, octadecyl. ammonium chloride, di-heptadecyl-imidazoline acetate of di-ethyl acetamide and the like.

Instead, use may be made of oils such as coconut oil,

palm oil, tallow oil, and the like, or their corresponding fatty acids and salts thereof soluble in the system in which the silicon resin is dissolved or dispersed therewith in an aqueous medium with suitable emulsifying agents.

Best use may be made of such lubricating compositions in amounts ranging from 0.1 to 3 percent by weight unless the organo-silicon resin is present in amounts substantially greater than 3 percent. In the latter circumstance, the amount of lubricant may be increased to about 5 percent by weight of the treating composition. Since the lubricant tends to soften the resinous material and impart softness to the hair, the amount should be balanced in consideration with the type of hair and in proportion to the amount of organo-silicon resin in the treating composition.

Since it is important to secure uniform penetration of the treating composition into the mass of hair being operated upon, and since most hair shafts naturally acquire a film of oil on the surfaces thereof, it has been found desirable to incorporate a small amount of wetting agent into the treating composition, or else to treat the hair in advance of its application with such surface active agents. As previously described, the wetting agent may comprise the substance used as a lubricant when compounded of organic groups having more than carbon atoms. Instead, use may be made of other surface active agents of the type of aryl alkyl polyether alcohols, such as are marketed by Rohm & Haas under the trade name Triton X100, or Atlas Powder Company under the trade name Tween, or sorbitan monolaurate, monopalmitate, or monostearate polyoxyethylene derivatives, polyglycol esters, dioctyl ester of sodium sulfosuccinate, alkyl naphthalene sulfonate, sorbitan, sulfooleate, fatty alcohol sulphates, aromatic polyglycol ethers, polyoxyethylene ethers, sodium di(2-ethyl-hexyl) phosphate, alkyl aryl sulfonates, and the like. The amount of wetting agent may range from 0.05 to 2 percent by weight of the treating composition. Although more can be used, the amount specified is sufiicient.

Description will now be made of the practice of this invention with the use of hot combs or other heating means to set the organo-silicon resin-forming material. In practice, it is best to shampoo the hair thoroughly to remove any dirt, grease, oil, or the like. After drying, the treating composition containing the organo-silicon compound in combination with a lubricant in suitable solvents or in aqueous dispersion is applied lightly to secure a homogeneous coverage on all sections of the hair, as by means of an atomizing spray, cotton swab, or distribution may be achieved by pouring the composition onto certain areas and working into the hair with the finger tips. The area of the hair which has been wetted with the treating composition is then straightened by use of a metallic comb heated to a temperature which exceeds 250 F. but is preferably maintained at a temperature within the range of 300400 F. The hair is pressed with the heated comb until all foaming caused by the rapid evaporation of diluent or water ceases and until any solvent odor has substantially completely disappeared. This may require only two to three passes of the hot comb through the hair during which time the diluent is eliminated and the resinous substance set on the hair fibers.

In any event, combing or heating for a time greater than from two to four minutes is seldom required, while in most practices heating for fractions of a second has been found to be sufficient.

Kinky hair which has been straightened by this new technique can be permanently waved simply by wrapping a shock of the straightened hair about curlers and then heating in the usual manner employed for permanent waving for a short length of time without requiring application of additional treating composition. Hair which is naturally straight can be permanently waved by wrapping shocks of hair about curlers in the normal permanent-wave technique, applying the organo-silicon containing treating composition herein described, and then heating for the usual length of time for driving off the solvent and advancing the resinous material. The time required by this process corresponds favorably with that generally emtaining catalysts which by condensation reaction or OXi-,

dation provides for the polymerization of the organosilicon on the hair fibers upon elimination of diluent. Thus the compositions may be applied and used with or without heat though the setting time is markedly advanced by the use of elevated temperatures.

In the technique described and claimed herein for setting the hair on the human head, it is unnecessary to eliminate the ingredients from the hair fibers from one application to another because the materials used are not injurious to the hair or scalp but, instead, tend to improve the quality and the characteristics of the hair by introducing softness, sheen and better handling properties. The technique described embodies a number of other advantages over systems heretofore employed by reason of the fact that the hair fibers do not become discolored nor are the hair molecules modified in any manner by reactions with the applied materials or by plasticization through the use of reducing agents and oxidizing agents.

The following examples of compositions which may be employed in the practice of this invention are given by way of illustration but not by way of limitation:

Example 1 15 percent by weight polysiloxane organo-silicon resin having a setting temperature between 250 and 500 F.

0.13 percent by weight organic lubricant 0O.4 percent by weight perfume oil 91.6-98.9 percent by weight diluent Example 2 1-3 percent by weight polysiloxane resin (phenyl ethyl,

phenyl and ethyl polysiloxane) 0.1-3 percent by weight stearato chromic chloride lubricant 0.1-0.4 percent by weight perfume oil 93.6-98.8 percent by weight diluent Exampz'e 3 13 percent by weight dimethyl phenyl and methyl polysiloxane curing at 300350 F.

0.13 percent by weight dicoco diethyl ammonium chloride O.1O.2 percent by weight perfume oil 25 percent by weight cellosolve 15 percent by weight xylol 53.858.8 percent by weight kerosene Example 4 3 percent by weight polysiloxane resin (phenyl and ethyl polysiloxane) 1.5 percent by weight palm oil 0.2 percent by weight sorbitan monolaurate polyoxyethylene derivative (dispersion agent) 95.3 percent by weight water Example 5 4 percent by weight polysiloxane resin (phenyl ethyl,

phenyl and ethyl polysiloxane) 3 percent by weight octadecyl ammonium chloride 0.2 percent by weight perfume oil 92.8 percent by weight ethylene glycol monoethyl ether Example 6 5.0 percent by weight polysiloxane resin (phenyl ethyl,

phenyl and ethyl polysiloxane) 4.0 percent by weight tallow oil 0.2 percent by weight perfume oil 40 percent by weight cellosolve 0.3 percent by weight dioctyl ester of sodium sulfosuccinate 50.5 percent by weight xylol The compositions of Examples 16 are adapted to be sprayed onto small sections of cleaned and dried hair, as by means of an atomizer. The wetted hair is combed with a metallic comb heated to about 300 F. by passing the comb three to four times slowly through the hair. The same steps are repeated on adjacent sections of hair until the entire head of hair has been treated. Kinky hair in this manner is made straight and provided with a very attractive sheen and appearance. After straightening, the hair may be finger-waved or pin-curled in the cold or else heated with heated curling irons or permanently waved with a permanent waving machine or else styled to the desired hair arrangement with or without the addition of treating composition. The hair may be exposed to moisture without causing reversion to its original kinky or uncurled state.

In the event that it is desired to achieve hair setting without the use of hot combs, compositions of the type provided in Example 1 may be employed with the addition of catalytic agents in small amounts ranging from 0.1 to 0.5 percent by weight to advance the organosilicon resin forming material in set stage in situ upon the hair during and subsequent to the elimination of diluent. Compositions of the type set forth in Example 1 may also have incorporated therein a dehydration catalyst of the type ethyl borate, ethylene diamine, triethan'olamine and the like, in amounts ranging from 0.1 to 1 percent by weight. Such catalytic agents are preferably introduced into the composition just prior to application onto the hair. When such catalytic agents are used, it has been found that the reactions take place more slowly than at elevated temperature but it is seldom necessary to use temperatures in excess of 200-250" F. to achieve the desired setting action in from 2060 seconds.

The following are further examples which specifically illustrate the use of compositions for setting hair principally by the evaporation of diluent:

Example 7 3.0 percent by weight polysiloxane resin of the type prov duced by United States Patent'No'. 2,371,068 2.0 percent by weight ditallow dimethyl ammonium chloride 0.2 percent by weight wetting agent 0.2 percent by weight perfume oil 68.5 percent by weight low boiling petroleum sol ent 26.1 percent by weight benzene Example 8 5.0 percent by weight polysiloxane resin (British Patent 2.0 percent by weight palm oil 0.3 percent by weight allyl alkyl polyethyl alcohol wetting agent 0.2 percent by weight perfume oil 0.2 percent by weight dispersing agent 92.3 percent by weight water The composition of Example 7 is prepared in the form of a solvent solution while the composition of Example 8 is prepared in the form of an aqueous dispersion.

The composition of Example 7 may be applied onto sections of the hair as by spraying or by swabbing with a cotton pad and the hair combed or otherwise maintained in position until the water or solvent has been substantially completely eliminated by evaporation. Elimination of the diluent may becarried out under room conditions limit is accelerated by the use ofelevated temperatures such as temperatures of about 100150' F. Higher temperatures may be used so long as the temperature does not exceed that at which the hair will be harmed.

It will be understood that invention herein resides in the composition as well' as in the method for applying'the compositions in the treatment of hair and it will be further understood that changes may be made in the materials, their amounts and their method of application without departing from the spirit of the invention, especially as defined inthe following claims.

I claim:

1. The method of setting hair on the human head comprising'the steps of treating the hair with an aqueous composition containing an organo-silicon resinous material and an organic surface active lubricant selected from the group consisting of vegetable oils, Werner complex compounds having an acido group containing at least 10 carbon atoms coordinated with a trivalent nuclear chromium atom, and a cationic amine having an organic group having more than 10 carbon atoms attached to a base amine group, and then heating the hair with the composition thereon to set the organo-silicon resin and the lubricant on the hair fibers while the hair is positioned in the arrangement in which it is desired to be set.

2. The method of setting hair comprising the steps of treating the hair with an aqueous dispersion containing 1 to 5 percent by weight of an organo-silicon resin and up to 3 percent by weight of a surface active organic lubricant selected from the group consisting of vegetable oils, Werner complex compounds having an acido group. containing at least 10 carbon atoms coordinated with a trivalent nuclear chromium atom, and a cationic amine having an organic group having more than 10 carbon atoms attached to a base amine group, and eliminating the aqueous medium from portions of the treated hair While positioning the hair in the arrangement in which it is to be set.

3. An aqueous composition for conditioning hair on the human head containing 1 to less than 5 percent by weight of an organo-silicon resin, and 0.1 to 3 percent by weight of a surface active organic lubricant selected from the group consisting of vegetable oils, Werner complex compounds having an acido group containing at least 10 carbon atoms coordinated with a trivalent nuclear chromium atom, and a cationic amine having an organic group having more than 10 carbon atoms attached to a base amine group.

4. An aqueous composition for conditioning hair onthe human head containing an organo-silicon resin and a surface active organic lubricant selected from the group consisting of vegetable oils, Werner complex compounds having an acido group containing at least 10 carbon atoms coordinated with a trivalent nuclear chromium atom and a cationic amine having an organic group having more than 10 carbon atoms attached to a base amine group.

References Cited in the file of this patent UNITED STATES PATENTS 1,055,972 Freeman Mar. 11, 1913 2,273,040 ller Feb. 17, 1942 2,356,161 ller Aug. 22, 1944 2,356,542 Sloan Aug. 22, 1944 2,390,073 Calva Dec. 4, 1945 2,392,805 Biefcld Jan. 15, 1946 2,405,041 Mathes July 30, 1946 2,544,668 Goebel Mar. 13, 1951, 2,643,375 Gant June 23, 1953 (Other references on following page) OTHER REFERENCES Silicone Notes, Dow Corning Corporation, Midland, Michigan, De Cetex 104, Ref. No. 1043, August 1, 1950, 6 pages;

Silicone Notes, Dow Corning Corporation, Midland, Michigan, DC 1107, Ref. No. 11071, October 4, 1949, 5 pages.

Silicone Notes, Dow Corning Corporation, Midland,

Michigan, De Cetex 104, Ref. No. 1042, August 1, 1949', 4 pages.

(Copies of the above Preliminary Data Sheets of Dow Corning Corporation are available in Division 50.)

Alexander et 211.: Application of Organosilicon Polymers to Wool. J. Soc., Dyers and Colourists, March 1949, pages 107 to 115. 

1. THE METHOD OF SETTING HAIR ON THE HUMAN HEAD COMPRISING THE STEPS OF TREATING THE HAIR WITH AN AQUEOUS COMPOSITION CONTAINING AN ORGANO-SILICON RESINOUS MATERIAL AND AN ORGANIC SURFACE ACTIVE LUBRICANT SELECTED FROM THE GROUP CONSISTING OF VEGETABLE OILS, WERNER COMPLEX COMPOUNDS HAVING AN ACIDO GROUP CONTAINING AT LEAST 10 CARBON ATOMS COORDINATED WITH A TRIVALENT NUCLEAR CHROMIUM ATOM, AND A CATIONIC AMINE HAVING AN ORGANIC GROUP HAVING MORE THAN 10 CARBON ATOMS ATTACHED TO A BASE AMINE GROUP, AND THEN HEATING THE HAIR WITH THE COMPOSITION THEREON TO SET THE ORGANO-SILICON RESIN AND THE LUBRICANT ON THE HAIR FIBERS WHILE THE HAIR IS POSITIONED IN THE ARRANGEMENT IN WHICH IT IS DESIRED TO BE SET. 